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1.
This research is part of a European project (namely, CODICE project), main objective of which is modelling, at a multi-scale, the evolution of the mechanical performance of non-degraded and degraded cementitious matrices. For that, a series of experiments were planned with pure synthetic tri-calcium silicate (C3S) and bi-calcium silicate (C2S) (main components of the Portland cement clinker) to obtain different calcium–silicate–hydrate (C–S–H) gel structures during their hydration. The characterization of those C–S–H gels and matrices will provide experimental parameters for the validation of the multi-scale modelling scheme proposed. In this article, a quantitative method, based on thermal analyses, has been used for the determination of the chemical composition of the C–S–H gel together with the degree of hydration and quantitative evolution of all the components of the pastes. Besides, the microstructure and type of silicate tetrahedron and mean chain length (MCL) were studied by scanning electron microscopy (SEM) and 29Si magic-angle-spinning (MAS) NMR, respectively. The main results showed that the chemical compositions for the C–S–H gels have a CaO/SiO2 M ratio almost constant of 1.7 for both C3S and C2S compounds. Small differences were found in the gel water content: the H2O/SiO2 M ratio ranged from 2.9 ± 0.2 to 2.6 ± 0.2 for the C3S (decrease) and from 2.4 ± 0.2 to 3.2 ± 0.2 for the C2S (increase). The MCL values of the C–S–H gels, determined from 29Si MAS NMR, were 3.5 and 4 silicate tetrahedron, for the hydrated C3S and C2S, respectively, remaining almost constant at all hydration periods.  相似文献   

2.
Differential scanning calorimetry data at different heating rates (5, 10, 15 and 20 °C min−1) of Se70Te15In15 chalcogenide glass is reported and discussed. The crystallization mechanism is explained in terms of recent analyses developed for use under non-isothermal conditions. The value of Avrami exponent (n) indicates that the glassy Se70Te15In15 alloy has three-dimensional growth. The average values of the activation energy for glass transition, E g, and crystallization process, E c, are (154.16 ± 4.1) kJ mol−1 and (98.81 ± 18.1) kJ mol−1, respectively. The ease of glass formation has also been studied. The reduced glass transition temperature (T rg), Hruby’ parameter (K gl) and fragility index (F i) indicate that the prepared glass is obtained from a strong glass forming liquid.  相似文献   

3.
We report herein a comprehensive study of the gas-phase Fe+-mediated oxidation of ethane by N2O on both the sextet and quartet potential energy surfaces (PESs) using density functional theory. The geometries and energies of all the relevant stationary points are located. Initial oxygen-atom transfer from N2O to iron yields FeO+. Then, ethane oxidation by the nascent oxide involves C–H activation forming the key intermediate of (C2H5)Fe+(OH), which can either undergo C–O coupling to Fe+ + ethanol or experience β-H shift giving the energetically favorable product of FeC2H4 + + H2O. Reaction of FeC2H4 + with another N2O constitutes the third step of the oxidation. N2O coordinates to FeC2H4 + and gets activated by the metal ion to yield (C2H4)Fe+O(N2). After releasing N2 through the direct H abstraction and/or cyclization pathways, the system would be oxidized to ethenol, acetaldehyde, and oxirane, regenerating Fe+. Oxidation to acetaldehyde along the cyclization –C–to–C hydrogen shift pathway is the most energetically favored channel.  相似文献   

4.
It is shown that palladium–cobalt oxide–cerium catalyst deposited on cordierite catalyzes the reduction of nitrogen(II) oxide with carbon monoxide, and cobalt–iron catalysts in simultaneous reduction of NO + N2O with C3-C4 alkanes retained high activity in the presence of water vapor and sulfur dioxide. The Pd-Co3O4/cordierite catalyst exceeds the Pt-Co3O4/codierite catalyst in the conversion of NO and CO in the reaction mixture CO + NO + O2 + H2O + SO2. Modification of the Pd-Co3O4/cordierite with cerium oxide considerably increases its sulfur resistance.  相似文献   

5.
Abstract  Formal [2 + 2 + 2] addition reaction of [Cp*Ru(H2O)(NBD)][BF4] (NBD = norbornadiene) with 4,4′-Diethynylbiphenyl generates [C9H96-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BF4]2. The reaction of [Cp*Ru(H2O)(NBD)][BF4] with 1,4-diphenylbutadiyne generates the unusual [2 + 2 + 2] additional organic compound Ph–C≡C–C9H8–Ph in addition to the organometallic compound [Cp*Ru(η6-C6H5–C≡C–C≡C–Ph)][BF4]. [C9H96-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BPh4]2 is generated after the reaction of compound [C9H96-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BF4]2 with Na[BPh4]. The structure of this compound was confirmed by X-ray diffraction. A possible approach to form Ph–C≡C–C9H8–Ph and [Cp*Ru(η6-C6H5–C≡C–C≡C–Ph)][BF4] is suggested. Graphical Abstract  Formal [2 + 2 + 2] addition reaction of [Cp*Ru(H2O)(NBD)]BF4 (NBD = norbornadiene) with 4,4′-Diethynylbiphenyl generates [C9H96-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BF4]2. The reaction of [Cp*Ru(H2O)(NBD)][BF4] with 1,4-diphenylbutadiyne simply generates unusual [2 + 2 + 2] additional organic compound Ph–C≡C–C9H8–Ph in addition to the organometallic compound [Cp*Ru(η6-C6H5–C≡C–C≡C–Ph)][BF4]. [C9H96-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BPh4]2 is generated after the reaction of compound [C9H96-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BF4]2 with Na[BPh4]. The structure of this compound was confirmed by X-ray diffraction. And the possible approach to form Ph–C≡C–C9H8–Ph and [Cp*Ru(η6-C6H5–C≡C–C≡C–Ph)][BF4] was suggested. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

6.
Electrolytes of 1 M blend salts (LiPF6 and tetraethylammonium tetrafluoroborate, Et4NBF4) have been investigated in supercapacitor battery system with composite LiMn2O4 and activated carbon (AC) cathode, and Li4Ti5O12 anode. The results obtained with the blend salts electrolytes are compared with those obtained with cells build using standard 1 M LiPF6 dissolved in ethylene carbonate + dimethyl carbonate + ethyl (methyl) carbonate (EC + DMC + EMC, 1:1:1 wt.%) as electrolyte. It is found that the blend salts electrolyte performs better on both electrochemical and galvanostatic cycling stability, especially cycled at 4 C rate. When the concentration of LiPF6 is 0.2 M and Et4NBF4 is 0.8 M, the capacity retention of the battery is 96.23% at 4 C rate after 5,000 cycles, much higher than that of the battery with standard 1 M LiPF6 electrolyte, which is only 62.35%. These results demonstrate that the blend salts electrolyte can improve the galvanostatic cycling stability of the supercapacity battery. Electrolyte of 0.2 M LiPF6 + 0.8 M Et4NBF4 in EC + DMC + EMC (1:1:1 wt.%) is a promising electrolyte for (LiMn2O4 + AC)/Li4Ti5O12.  相似文献   

7.
Homogeneous manganocolumbite (MnNb2O6) was synthesized from Nb2O5 and MnO oxides. Powder sample was orthorhombic with unit cell parameters: α = 0.5766 nm, b = 1.4439 nm, c = 0.5085 nm and V = 0.4234 nm3. Heat capacity over the temperature range of 313–1253 K was measured in an inert atmosphere with combined thermogravimetry and calorimetry using NETZSCH STA 449C Jupiter thermoanalyzer. Melting point was 1767 ± 3 K, enthalpy of melting was 144 ± 4 kJ mol−1. Experimental heat capacity of MnNb2O6 is fitted to polynomial C pm = 221.46 + 3.03 · 10−3 T + −39.79 · 105 T −2 + 40.59 · 10−6 T 2.  相似文献   

8.
To test the feasibility of local spin theory of Davidson and Clark for ferrodoxin clusters, the models [Fe2S2(SR)4]2− (R=—H, —CH3) are chosen for evaluation. This purpose is realized by calculating the local spin expectation values 〈S A·S B〉, 〈S A 2 〉, and m A and discussing the connection between these expected values and the Heisenberg spin model (HSM) and the Noodleman broken-symmetry approach. In practical calculation, the spin-unrestricted Hartree-Fock (UHF) and spin-polarized density functional theory (DFT) are used and the calculational qualities of these two methods are also discussed. In addition, the theoretical magnetic coupling constants J AB of these models are calculated by various computational schemes for comparison with both theoretical and experimental results previously reported. Supported by the Doctorial Initial Foundations of Hainan Normal University (Grant No. 13140252)  相似文献   

9.
The complex of [Nd(BA)3bipy]2 (BA = benzoic acid; bipy = 2,2′-bipyridine) has been synthesized and characterized by elemental analysis, IR spectra, single crystal X-ray diffraction, and TG/DTG techniques. The crystal is monoclinic with space group P2(1)/n. The two–eight coordinated Nd3+ ions are linked together by four bridged BA ligands and each Nd3+ ion is further bonded to one chelated bidentate BA ligand and one 2,2′-bipyridine molecule. The thermal decomposition process of the title complex was discussed by TG/DTG and IR techniques. The non-isothermal kinetics was investigated by using double equal-double step method. The kinetic equation for the first stage can be expressed as dα/dt = A exp(−E/RT)(1 − α). The thermodynamic parameters (ΔH , ΔG , and ΔS ) and kinetic parameters (activation energy E and pre-exponential factor A) were also calculated.  相似文献   

10.
The photodissociation of ethyl iodide at 279.71, 281.73, 304.02 and 304.67 nm has been studied on our new mini-photofragment translational spectrometer with a total flight path of only 5 cm. Some vibrational peaks are firstly resolved in the TOF spectra of I*(2P1/2) and I(2P3/2) channels. These vibrational peaks are assigned to the excitation states (v2 = 0, 1, 2,…) of the umbrella mode (v2, 540 cm-1) of the photofragment C2H5, and the distribution of the vibrational states is obtained. The dissociation energy has been determined to be D0(C-I)=2.314 ±0.03 eV. The energy partitioning of the available energy (Eavl=ET Eint=ET EV,R) calculated from our experimental data (-E)int/Eavl= 22.1% at 281.73 nm, 22.4% at 304.02 nm for the I* channel, and (-E)int/Eavl = 25.2% at 279.71 nm, 25.9% at 304.67 nm for the I channel, seem to be more reliable.  相似文献   

11.
Fullerenyl radicals (FR) RC60 · and chemiluminescence (CL) are generated in the presence of O2 in C60—R3Al (R = Et, Bui) solutions in toluene (T = 298 K). The FR are formed due to the addition of the R· radical, which is an intermediate of R3Al autooxidation, to C60. Mass spectroscopy and HPLC were used to identify EtnC60Hm (n, m = 1–6), EtpC60 (p = 2–6), and dimer EtC60C60Et as stable products of FR transformations. As found by ESR, the EtC60 · radical (g = 2.0037) is also generated by photolysis of solutions obtained after interaction in the (C60— R3Al)—O2 system. In the presence of dioxygen, the FR is not oxidized but yields complexes with O2, which appear as broadening of the ESR signals. Chemiluminescence arising in the (C60—R3Al)—O2 system is much brighter (I max = 1.86·108 photon s−1 mL−1) than the known background CL (I max = 6.0·106 photon s−1 mL−1) for the autooxidation of R3Al and is localized in a longer-wavelength spectral region (λmax = 617 and 664 nm). This CL is generated as a result of energy transfer from the primary emitter 3CH3CHO* to the products of FR transformation: RnC60Hm, RpC60, and EtC60C60Et. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 205–213, February, 2007.  相似文献   

12.
Summary.  Single crystals of MgAl2F8(H2O)2 have been obtained under hydrothermal conditions (250°C, 14 d) from a starting mixture of AlF3 and MgAlF5(H2O)2 in a 5% (w/w) HF solution. The crystal structure has been determined and refined from single crystal data (Fmmm (#69), Z = 4, a = 7.2691(7), b = 7.0954(16), c = 12.452(2) ?, 281 structure factors, 27 parameters, R(F 2 > 2σ (F 2)) = 0.0282, wR(F 2 all) = 0.0885). The obtained crystals were systematically twinned according to (010/100/001) as twinning matrix, reflecting the pseudo-tetragonal metric. The crystal structure is composed of perowskite-type layers built of corner sharing AlF6 octahedra with an overall composition of AlF4 which are connected via common fluorine atoms of [MgF4/2(H2O)2/1] octahedra. Group-subgroup relations of MgAl2F8(H2O)2 to WO3(H2O)0.33 and to other M(II)M(III)2 F8(H2O)2 structures are briefly discussed. Above 570°C, MgAl2F8(H2O)2 decomposes under elimination of water into α-AlF3, β-AlF3, and MgF2. Received October 29, 2001. Accepted (revised) December 6, 2001  相似文献   

13.
From extraction experiments and γ-activity measurements, the exchange extraction constant corresponding to the equilibrium Ag+(aq) + 1⋅Cs+(nb) ⇆ 1⋅Ag+(nb) + Cs+(aq) taking part in the two-phase water–nitrobenzene system (where 1 = hexaarylbenzene-based receptor; aq = aqueous phase, nb = nitrobenzene phase) was evaluated to be log 10 K ex(Ag+, 1⋅Cs+) = −1.0±0.1. Further, the stability constant of the hexaarylbenzene-based receptor⋅Ag+ complex (abbreviation 1⋅Ag+) in nitrobenzene saturated with water, was calculated at a temperature of 25 °C: log 10 β nb(1⋅Ag+) = 5.5±0.2. By using quantum mechanical DFT calculations, the most probable structure of the 1⋅Ag+ complex species was solved. In this complex having C3 symmetry, the cation Ag+ synergistically interacts with the polar ethereal oxygen fence and with the central hydrophobic benzene ring via cation–π interaction.  相似文献   

14.
We have established and analyzed the sequences of phase transitions in synthesis of layered compounds in the AnBn–1O3n family ( \textA3\textII\textLnB3\textV\textO12 {\text{A}}_3^{\text{II}}{\text{LnB}}_3^{\text{V}}{{\text{O}}_{{12}}} (AII = Ba, Sr, Ln = La, Nd, BV = Nb, Ta) and La4Ti3O12 with n = 4) from coprecipitated hydroxocarbonate and hydroxide systems, including steps involving the formation, solid-phase reaction, or structural rearrangement of intermediates.  相似文献   

15.
Structural information on free transition metal doped aluminum clusters, Al n TM + (TM = Ti, V, Cr), was obtained by studying their ability for argon physisorption. Systematic size (n = 5 – 35) and temperature (T = 145 – 300 K) dependent investigations reveal that bare Al n + clusters are inert toward argon, while Al n TM + clusters attach one argon atom up to a critical cluster size. This size is interpreted as the geometrical transition from surface-located dopant atoms to endohedrally doped aluminum clusters with the transition metal atom residing in an aluminum cage. The critical size, n crit , is found to be surprisingly large, namely n crit = 16 and n crit = 19 – 21 for TM = V, Cr, and TM = Ti, respectively. Experimental cluster–argon bond dissociation energies have been derived as function of cluster size from equilibrium mass spectra and are in the 0.1–0.3 eV range.  相似文献   

16.
Synthesis, characterization and thermal analysis of polyaniline (PANI)/ZrO2 composite and PANI was reported in our early work. In this present, the kinetic analysis of decomposition process for these two materials was performed under non-isothermal conditions. The activation energies were calculated through Friedman and Ozawa-Flynn-Wall methods, and the possible kinetic model functions have been estimated through the multiple linear regression method. The results show that the kinetic models for the decomposition process of PANI/ZrO2 composite and PANI are all D3, and the corresponding function is ƒ(α)=1.5(1−α)2/3[1−(1-α)1/3]−1. The correlated kinetic parameters are E a=112.7±9.2 kJ mol−1, lnA=13.9 and E a=81.8±5.6 kJ mol−1, lnA=8.8 for PANI/ZrO2 composite and PANI, respectively.  相似文献   

17.
Nano-composites of SnO(V2O3) x (x = 0, 0.25, and 0.5) and SnO(VO)0.5 are prepared from SnO and V2O3/VO by high-energy ball milling (HEB) and are characterized by X-ray diffraction (XRD), scanning electron microscopy, and high-resolution transmission electron microscopy techniques. Interestingly, SnO and SnO(VO)0.5 are unstable to HEB and disproportionate to Sn and SnO2, whereas HEB of SnO(V2O3) x gives rise to SnO2.VO x . Galvanostatic cycling of the phases is carried out at 60 mA g−1 (0.12 C) in the voltage range 0.005–0.8 V vs. Li. The nano-SnO(V2O3)0.5 showed a first-charge capacity of 435 (±5) mAh g−1 which stabilized to 380 (±5) mAh g−1 with no noticeable fading in the range of 10–60 cycles. Under similar cycling conditions, nano-SnO (x = 0), nano-SnO(V2O3)0.25, and nano-SnO(VO)0.5 showed initial reversible capacities between 630 and 390 (±5) mAh g−1. Between 10 and 50 cycles, nano-SnO showed a capacity fade as high as 59%, whereas the above two VO x -containing composites showed capacity fade ranging from 10% to 28%. In all the nano-composites, the average discharge potential is 0.2–0.3 V and average charge potential is 0.5–0.6 V vs. Li, and the coulombic efficiency is 96–98% after 10 cycles. The observed galvanostatic cycling, cyclic voltammetry, and ex situ XRD data are interpreted in terms of the alloying–de-alloying reaction of Sn in the nano-composite “Sn-VO x -Li2O” with VO x acting as an electronically conducting matrix.  相似文献   

18.
 It is argued that the preservation of algebraic equivalence between the Allen and Laidler bond-energy schemes for nonconjugated alkenes logically determines that the Allen scheme should apply to a classical structure of a conjugated hydrocarbon exactly as it stands, i.e. no additional parameters are needed. Extending the requirement of equivalence to conjugated alkenes implies that, in the Laidler scheme, the bond energy of the pure single CC bond in a conjugated system is a combination of the bond-energies of the semiconjugated and normal CC single bonds: E(Cd—Cd)=2E(Cd—C)−E(C—C). This result is a deduction and is not an independent hypothesis. The equivalence of the two schemes for conjugated hydrocarbons is demonstrated numerically, by calculating the resonance energies of some selected molecules by both methods. Received: 5 December 1999 / Accepted: 5 March 2000 / Published online: 5 June 2000  相似文献   

19.
The A1, O, AlO, A12O, Al2O2, WO2, and WO3, partial pressures in the vapor over Al2O3 in a tungsten Knudsen effusion cell between 2300 and 2600 K were derived from A1+, O+, AlO+, A12O+, Al2O2+, WO2+, and WO3+, ion intensities. The mass spectrometer was calibrated against the equilibrium constant of the WO3(g) = WO2(g) + O(g) reaction. Refined values of the ionization cross sections of AlO and A12O2 were used in the partial pressure calculations. The enthalpies of atomization of aluminum suboxides were determined to be Δat H o(AlO, g, 0) = 510.7 ± 3.3 kJ mol−1, Δat H o(Al2O, g, 0) = 1067.2 ± 6.9 kJ mol−1, and Δat H o(Al2O2, g, 0) = 1556.7 ± 9.9 kJ mol−1.  相似文献   

20.
Solubility product (Lu(OH)3(s)⇆Lu3++3OH) and first hydrolysis (Lu3++H2O⇆Lu(OH)2++H+) constants were determined for an initial lutetium concentration range from 3.72·10−5 mol·dm−3 to 2.09·10−3 mol·dm−3. Measurements were made in 2 mol·dm−3 NaClO4 ionic strength, under CO2-free conditions and temperature was controlled at 303 K. Solubility diagrams (pLuaq vs. pC H) were determined by means of a radiochemical method using 177Lu. The pC H for the beginning of precipitation and solubility product constant were determined from these diagrams and both the first hydrolysis and solubility product constants were calculated by fitting the diagrams to the solubility equation. The pC H values of precipitation increases inversely to [Lu3+]initial and the values for the first hydrolysis and solubility product constants were log10 β* Lu,H = −7.92±0.07 and log10 K*sp,Lu(OH)3 = −23.37±0.14. Individual solubility values for pC H range between the beginning of precipitation and 8.5 were S Lu3+ = 3.5·10−7 mol·dm−3, S Lu(OH)2+ = 6.2·10−7 mol·dm−3, and then total solubility was 9.7·10−7 mol·dm−3.  相似文献   

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